Controlling the Redox Activity of Quantum Dots with their Organic Adlayers
Emily Weiss a, Kedy Edme a, Stephen Jensen a, David Weinberg a
a Department of Chemistry, Northwestern University, United States, Sheridan Road, 2145, Evanston, United States
Materials for Sustainable Development Conference (MATSUS)
Proceedings of nanoGe September Meeting 2015 (NFM15)
Santiago de Compostela, Spain, 2015 September 6th - 15th
Invited Speaker, Emily Weiss, presentation 005
Publication date: 8th June 2015

Quantum dots emerge from the reaction mixture and subsequent purification coated with approximately a monolayer of organic ligands, which we refer to as “native ligands”. The native ligand shell that solubilizes and electronically passivates a QD also presents a physical barrier that impedes a molecule’s approach to the QD surface, and limits the number of available sites per QD for its adsorption. The ligand shell therefore acts as a semi-permeable self-assembled monolayer (SAM). For solid state electronics applications of nanoparticles (NPs), it makes sense to design NP films with as little organic material as possible without sacrificing passivation of the particle surfaces, because the organic material is, in general, electrically insulating. If, however, we are to use NPs in analytical, therapeutic, or photocatalytic applications, then we need to control 1) the interaction of the NP with proximate molecules of interest while minimizing non-specific or unproductive interactions, and 2) the stability of the monolayer in various chemical environments (for example, biological environments or chemically corrosive environments). Chemical functionalization of NPs is the most versatile, precisely tunable method for controlling the reactivity of a NP, because SAMs have been shown to act as molecular recognition layers. Here, we describe various ways to design a SAM to control its permeability to small molecules, some techniques to probe this permeability, and an application to photocatalysis of a multi-electron reaction.



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